Organic silver complexes, their preparation methods and their methods for forming thin layers

ABSTRACT

Provided herein is a method for preparing a silver complex. The method includes reacting a silver oxide with a mixture of ammonium carbamate and isopropyl amine at room temperature in the presence of methanol.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. patent applicationSer. No. 14/060,079, filed Oct. 22, 2013, which is a continuation ofU.S. patent application Ser. No. 13/469,412 filed May 11, 2012, which isa continuation of U.S. patent application Ser. No. 11/815,745, filedAug. 7, 2007, which is the National Stage of PCT/KR2006/000451, filedFeb. 7, 2006, and claims priority to Korean Patent Application No.10-2005-011478, filed Feb. 7, 2005, Korean Patent Application No.10-2005-0011631, filed Feb. 11, 2005, and Korean Patent Application No.10-2006-0011083, filed Feb. 6, 2006, the disclosures of each of whichare incorporated herein by reference in their entireties.

TECHNICAL FIELD

The present invention relates to a novel organic silver complex preparedby reacting a silver compound with an ammonium carbamate compound or anammonium carbonate compound and a preparation method thereof.

BACKGROUND ART

According to Ullmann's Encyclopedia of Ind. Chem., Vol. A24, 107(1993),silver is a precious metal resistant to oxidation, with superiorelectrical and thermal conductivity and catalytic and antibioticactivity. Thus, silver and silver compounds are widely used in alloys,plating, medicine, photography, electricity and electronics, fibers,detergents, household appliances, and so forth.

Silver compounds can be used as catalyst in synthesis of organiccompounds and polymers. Especially, with the recent regulation of use oflead in electric and electronic circuits, use of silver inlow-resistance metal wirings, printed circuit boards (PCB), flexibleprinted circuit boards (FPC), antennas for radio frequencyidentification (RFID) stags, plasma display panels (PDP), liquid crystaldisplays (TFT-LCD), organic light emitting diodes (OLED), flexibledisplays and organic thin-film transistors (OTFT) as metal patterns orelectrodes is on the increase.

Mostly, silver is used in the form of a paste comprising silver powder,a binder and a solvent. Or, a silver compound such as silver nitrate isreacted with another compound in an aqueous solution or an organicsolvent to obtain a variety of silver compounds or organic silvercompounds containing nanoparticles. These organic silver compounds areused to form metal patterns by chemical vapor deposition (CVD), plasmavapor deposition, sputtering, electroplating, photolithography, electronbeam technique, laser technique, etc.

The most common coordinator for organic silver complexes is carboxylicacid (Prog. Inorg. Chem., 10, p. 233(1968)). However, becausesilver-containing metal carboxylate complexes are generally sensitive tolight, hardly soluble in organic solvents (J. Chem. Soc., (A)., p. 514(1971), U.S. Pat. No. 5,534,312 (Jul. 9, 1996)) and have a highdecomposition temperature, they are limited in application in spite ofeasiness in preparation. To solve this problem, several methods havebeen proposed in J. Inorg. Nucl. Chem., 40, p. 1599 (1978), Ang. Chem.,Int. Ed. Engl., 31, p. 770 (1992), Eur. J. Solid State Inorg. Chem., 32,p. (1995), J. Chem. Cryst., 26, p. 99 (1996), Chem. Vapor Deposition, 7,111 (2001), Chem. Mater., 16, 2021 (2004), U.S. Pat. No. 5,705,661 (Jan.6, 1998) and Korean Patent No. 2003-0085357 (Nov. 5, 2003). Among themare the methods of using carboxylic acid compounds having long alkylchains or including amine compounds or phosphine compounds. However, thesilver derivatives known thus far are limited and have insufficientstability or solubility. Moreover, they have a high decompositiontemperature to be applied for pattern formation and are decomposedslowly.

U.K. Patent No. 609,807 published in 1948 discloses a method of reactingammonium carbonate or ammonium carbamate with a transition metal salt toobtain a transition metal salt coordinated by ammonia as carbon dioxideis generated. The patent mentions that silver complexes coordinated byammonia can be prepared by the method. However, surprisingly, thepresent inventors found out that when ammonium carbonate or ammoniumcarbamate is added to a silver compound such as silver oxide, a stablesilver complex is obtained without generation of carbon dioxide. Theyalso confirmed that the silver complex is isolated as solid and can beeasily prepared into thin film.

The silver complexes of the present invention are characterized in that,because they can be prepared under various reaction conditions, theyhave superior stability and solubility, can be easily prepared into thinfilm, thus enabling ease metal patterning, and are decomposed at lowtemperature, thus being easily prepared into thin film or powder.

DISCLOSURE OF THE INVENTION

It is an object of the present invention to provide a novel organicsilver complex obtained by reacting a silver compound with an ammoniumcarbamate compound or an ammonium carbonate compound and a preparationmethod thereof.

It is another object of the present invention to provide a novel organicsilver complex having superior stability and solubility and being easilyprepared into thin film and a preparation method thereof.

It is still another object of the present invention to provide a novelorganic silver complex which enables formation of high-purity metal filmsince it is decomposed at low temperature and a preparation methodthereof.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the ¹H NMR spectrum of the silver complex of Example 1.

FIG. 2 is the ¹³C NMR spectrum of the silver complex of Example 1.

FIG. 3 is the IR spectrum of the silver complex of Example 1.

FIG. 4 is the TGA thermogram of the silver complex of Example 1.

FIG. 5 is the DSC thermogram of the silver complex of Example 1.

FIG. 6 is the ¹H NMR spectrum of the silver complex of Example 23.

FIG. 7 is the ¹³C NMR spectrum of the silver complex of Example 23.

FIG. 8 is the IR spectrum of the silver complex of Example 23.

FIG. 9 is the TGA thermogram of the silver complex of Example 23.

FIG. 10 is the DSC thermogram of the silver complex of Example 23.

FIG. 11 is the ¹H NMR spectrum of the silver complex of Example 24.

FIG. 12 is the ¹³C NMR spectrum of the silver complex of Example 24.

FIG. 13 is the IR spectrum of the silver complex of Example 24.

FIG. 14 is the TGA thermogram of the silver complex of Example 24.

FIG. 15 is the DSC thermogram of the silver complex of Example 24.

BEST MODE FOR CARRYING OUT THE INVENTION

In order to attain the objects, the present inventors invented novelorganic silver complexes by reacting the silver compound represented bythe formula 2 below with the ammonium carbamate compound or ammoniumcarbonate compound represented by the formula 3, 4 or 5 below:

wherein, in the formula 2, n is an integer from 1 to 4, X is oxygen,sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate,phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate,acetylacetonate or carboxylate (For example, the silver compound may besilver oxide, thiocyanate, silver sulfide, silver chloride, silvercyanide, silver cyanate, silver carbonate, silver nitrate, silvernitrite, silver sulfate, silver phosphate, silver perchlorate, silvertetrafluoroborate, silver acetylacetonate, silver acetate, silverlactate, silver oxalate or a derivative thereof. Silver oxide or silvercarbonate is preferred with regard to reactivity or post-treatment,although not limited to them.), and

in the formulas 3 to 5, each of R₁, R₂, R₃, R₄, R₅ and R₆ isindependently hydrogen, C₁-C₃₀ aliphatic or cycloaliphatic alkyl, arylor aralkyl, substituted alkyl or aryl, where R₁ and R₂ and,independently, R₄ and R₅ may form an alkylene ring containing or notcontaining a hetero atom, a polymer compound or a derivative thereof(Although not limiting the present invention, it is preferred that eachof R₁ and R₄ is C₁-C₁₄ aliphatic alkyl and each of R₃, R₄, R₅ and R₆ ishydrogen or C₁-C₁₄ aliphatic alkyl).

Specifically, in the formulas 3 to 5, each of R₁, R₂, R₃, R₄, R₅ and R₆may be hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,amyl, hexyl, ethylhexyl, heptyl, octyl, isooctyl, nonyl, decyl, dodecyl,hexadecyl, octadecyl, docodecyl, cyclopropyl, cyclopentyl, cyclohexyl,allyl, hydroxy, methoxy, methoxyethyl, methoxypropyl, cyanoethyl,ethoxy, butoxy, hexyloxy, methoxyethoxyethyl, methoxyethoxyethoxyethyl,hexamethyleneimine, morpholine, piperidine, piperazine, ethylenediamine,propylenediamine, hexamethylenediamine, triethylenediamine, pyrrole,imidazole, pyridine, carboxymethyl, trimethoxysilylpropyl,triethoxysilylpropyl, phenyl, methoxyphenyl, cyanophenyl, phenoxy,tolyl, benzyl, a derivative thereof, a polymer compound such aspolyallylamine and polyethyleneimine or a derivative thereof, but notparticularly limited to them.

The ammonium carbamate compound represented by the formula 3 may be, forexample, ammonium carbamate, ethylammonium ethylcarbamate,isopropylammonium isopropylcarbamate, n-butylammonium n-butylcarbamate,isobutylammonium isobutylcarbamate, t-butylammonium t-butylcarbamate,2-ethylhexylammonium 2-ethylhexylcarbamate, octadecylammoniumoctadecylcarbamate, 2-methoxyethylammonium 2-methoxyethylcarbamate,2-cyanoethylammonium 2-cyanoethylcarbamate, dibutylammoniumdibutylcarbamate, dioctadecylammonium dioctadecylcarbamate,methyldecylammonium methyldecylcarbamate, hexamethyleneiminiumhexamethyleneiminecarbamate, morpholinium morpholinecarbamate,pyridinium ethylhexylcarbamate, triethylenediaminiumisopropylbicarbamate, benzylammonium benzylcarbamate,triethoxysilylpropylammonium triethoxysilylpropylcarbamate, etc.

For the ammonium carbamate compound of the present invention, onesubstituted by primary amine is preferred to those substituted bysecondary or tertiary amine in terms of reactivity and stability.

The ammonium carbonate compound represented by the formula 4 or formula5 may be, for example, ammonium carbonate, ammonium bicarbonate,ethylammonium ethylcarbonate, isopropylammonium isopropylcarbonate,isopropylammonium bicarbonate, n-butylammonium n-butylcarbonate,isobutylammonium isobutylcarbonate, t-butylammonium t-butylcarbonate,t-butylammonium bicarbonate, 2-ethylhexylammonium 2-ethylhexylcarbonate,2-ethylhexylammonium bicarbonate, 2-methoxyethylammonium2-methoxyethylcarbonate, 2-methoxyethylammonium bicarbonate,2-cyanoethylammonium 2-cyanoethylcarbonate, 2-cyanoethylammoniumbicarbonate, octadecylammonium octadecylcarbonate, dibutylammoniumdibutylcarbonate, dioctadecylammonium dioctadecylcarbonate,dioctadecylammonium bicarbonate, methyldecylammoniummethyldecylcarbonate, hexamethyleneiminium hexamethyleneiminecarbonate,morpholinium morpholinecarbonate, benzylammonium benzylcarbonate,triethoxysilylpropylammonium triethoxysilylpropylcarbonate, pyridiniumbicarbonate, triethylenediaminium isopropylcarbonate,triethylenediaminium bicarbonate or a derivative thereof.

The ammonium carbamate compound, the ammonium carbonate compound andpreparation method thereof are not particularly limited. For example, J.Am. Chem. Soc., 70, p. 3865 (1948), J. Am. Chem. Soc., 73, p. 1829(1951), J. Prakt. Chem., 9, p. 217 (1959), J. Am. Chem. Soc., 123, p.10393 (2001), Langmuir, 18, 7124 (2002) and U.S. Pat. No. 4,542,214(Sep. 17, 1985) disclose that the compounds can be prepared from primaryamine, secondary amine, tertiary amine or a mixture thereof and carbondioxide. According to the disclosure, an ammonium carbonate compound isobtained if 0.5 mole of carbon dioxide is used per 1 mole of amine andan ammonium bicarbonate compound is obtained if more than 1 mole ofcarbon dioxide is used per 1 mole of amine. The preparation may beperformed under normal pressure or applied pressure with or without asolvent. When a solvent is used, an alcohol such as methanol, ethanol,isopropanol and butanol, a glycol such as ethylene glycol and glycerine,an acetate such as ethyl acetate, butyl acetate and carbitol acetate, anether such as diethyl ether, tetrahydrofuran and dioxane, a ketone suchas methyl ethyl ketone and acetone, a hydrocarbon solvent such as hexaneand heptane, an aromatic solvent such as benzene and toluene, ahalogen-substituted solvent such as chloroform, methylene chloride andcarbon tetrachloride, etc. may be used. Carbon dioxide may be bubbled inthe gas phase or solid dry ice may be used. The reaction may beperformed in the supercritical state. Any other known methods can beapplied for the preparation of the ammonium carbamate derivative and theammonium carbonate derivative, as long as the structure of the targetcompound is the same. That is, preparation solvent, reactiontemperature, concentration, catalyst, etc. are not particularly limited.And, the preparation yield is irrelevant of the preparation method.

Such prepared ammonium carbamate compound or ammonium carbonate compoundis reacted with the silver compound to obtain the organic silvercomplex. For example, at least one silver compound represented by theformula 2 may be reacted with at least one ammonium carbamate derivativeor ammonium carbonate derivative represented by the formulas 3 to 5under nitrogen atmosphere at normal pressure or applied pressure with orwithout a solvent. When a solvent is used, an alcohol such as methanol,ethanol, isopropanol and butanol, a glycol such as ethylene glycol andglycerine, an acetate such as ethyl acetate, butyl acetate and carbitolacetate, an ether such as diethyl ether, tetrahydrofuran and dioxane, aketone such as methyl ethyl ketone and acetone, a hydrocarbon solventsuch as hexane and heptane, an aromatic solvent such as benzene andtoluene, halogen-substituted solvent such as chloroform, methylenechloride and carbon tetrachloride, etc. may be used. However, thesolvent used in the preparation of the organic silver complex of thepresent invention needs not be particularly limited. That is, any othersolvent may be used as long as the structure of the target compound isthe same.

The silver complex of the present invention has the structurerepresented by the following formula 1:Ag[A]_(m)  (1)

where A is the compound represented by the formula 3, 4 or 5 and0.7≦m≦2.5.

The silver complexes of the present invention are isolated as whitesolid. When decomposed by heating, the resultant compounds containconductive, non-valent silver, not in the oxidized state. The IRspectrums (FIG. 3, FIG. 8 and FIG. 13) of the silver complexes show C═Oabsorption bands and confirms that carbon dioxide is not produced. The¹H NMR spectrums (FIG. 1, FIG. 6 and FIG. 11) and the ¹³C NMR spectrums(FIG. 2, FIG. 7 and FIG. 12) also confirm the functional groups of theammonium carbamate compound or the ammonium carbonate compound.

The silver complexes of the present invention show specific meltingpoints and decomposition patterns as seen in the TGA thermograms and theDSC thermograms (FIG. 4, FIG. 5, FIG. 9, FIG. 10, FIG. 14 and FIG. 15).When the melt silver complexes are cooled, stable solid silver complexesare obtained.

The organic silver complex of the present invention is highly soluble ina variety of solvents including ones used to prepare the organic silvercomplex, for example, an alcohol such as methanol, an ester such asethyl acetate, an ether such as tetrahydrofuran, etc. Thus, the silvercomplex can be readily used in coating or printing and can be stablystored in the form of solution for over 3 months.

The organic silver complex solution may be prepared into thin film bycoating on a substrate of glass, silicon wafer, polymer film likepolyester and polyimide, paper, etc. or printed directly. The thin filmformation may be performed by spin coating, roll coating, spray coating,dip coating, flow coating, etc. And, the printing may be performed byink-jet printing, offset printing, screen printing, gravure printing,flexo printing, etc.

The prepared thin film may be oxidized, reduced or heat-treated or theorganic silver complex may be treated with chemical vapor deposition(CVD), plasma vapor deposition, sputtering, electroplating, lithography,IR, electron beam or laser to obtain a metal or metal oxide pattern. Theheat treatment may be performed under inert gas atmosphere, as usually,but also may be performed in air or using a mixture gas of hydrogen andair or other inert gas.

Hereinafter, the present invention is described in further detailthrough examples. However, the following examples are only for theunderstanding of the present invention and the present invention is notlimited to or by them.

EXAMPLES Example 1 Reaction of silver oxide with 2-ethylhexylammonium2-ethylhexylcarbamate

In a 50 mL Schlenk flask equipped with a stirrer, 3.25 g (10.75 mmol) of2-ethylhexylammonium 2-ethylhexylcarbamate (viscous liquid) wasdissolved in 10 mL of methanol. 1.0 g (4.31 mmol) of silver oxide wasadded and reaction was performed at room temperature. The reactionsolution was initially a black slurry but it turned transparent ascomplex was produced. After 2 hours of reaction, a colorless,transparent solution was obtained. The resultant solution was filteredwith a 0.45 micron membrane filter to remove unreacted silver oxide.Then, the solvent was removed at vacuum to obtain white solid. The solidwas recrystallized in ethyl acetate, dried and weighed to obtain 4.22 gof a silver complex (yield=99.4%). The silver complex had a meltingpoint of 57-58° C. (DSC=57.26° C.) and a silver content of 22.0 wt %(TGA analysis).

¹H NMR (CD₃OD, ppm), 1.11-1.19 (m, —CH₃) 1.51-1.69 (m, —CH₂, —CH),2.91-2.92, 3.23-3.25 (d, —NCH₂), 5.13 (s, —NH₂), ¹³C NMR (CD₃OD, ppm),166.09, 47.60, 44.24, 31.76, 30.12, 24.77, 24.30, 14.64, 11.15

Example 2 Reaction of Silver Oxide with n-propylammoniumn-propylcarbamate

In a 50 mL Schlenk flask equipped with a stirrer, 1.74 g (10.75 mmol) ofn-propylammonium n-propylcarbamate (viscous liquid, melting point:74-76° C.) was dissolved in 10 mL of methanol. 1.0 g (4.31 mmol) ofsilver oxide was added and reaction was performed at room temperaturefor 2 hours while stirring. A colorless, transparent complex solutionwas obtained as in Example 1. The resultant solution was filtered with a0.45 micron membrane filter to remove and the solvent was removed atvacuum to obtain white solid. The solid was dried and weighed to obtain2.42 g of a silver complex (yield=88.3%). Most of the silver complex wasdecomposed below 130° C. to leave metallic silver. The silver contentwas 38.4 wt % (TGA analysis). ¹H NMR (CD₃OD, ppm), 0.98-1.02 (t, —CH₃)1.59-1.65 (m, —CH₂), 2.76-2.80 (t, —NCH₂), ¹³C NMR (CD₃OD, ppm), 47.03,27.84, 11.53

Example 3 Reaction of Silver Oxide with IsopropylammoniumIsopropylcarbamate

In a 50 mL Schlenk flask equipped with a stirrer, 1.60 g (10.75 mmol) ofisopropylammonium isopropylcarbamate (white solid, melting point: 78-80°C.) was dissolved in 10 mL of methanol. 1.0 g (4.31 mmol) of silveroxide was added and reaction was performed at room temperature. Thereaction solution was initially a black slurry but it turned transparentas complex was produced. After 2 hours of reaction, a colorless,transparent solution was obtained. The resultant solution was filteredwith a 0.45 micron membrane filter and the solvent was removed at vacuumto obtain white solid. The solid was dried and weighed to obtain 2.48 gof a silver complex (yield=95.5%). Most of the silver complex wasdecomposed below 130° C. to leave metallic silver. The silver contentwas 37.2 wt % (TGA analysis).

¹H NMR (CD₃OD, ppm), 1.13-1.22 (d, —CH₃), 3.22-3.31 (m, CH), ¹³C NMR(CD₃OD, ppm), 45.78, 26.06

Example 4 Reaction of Silver Oxide with n-butylammonium n-butylcarbamate

In a 50 mL Schlenk flask equipped with a stirrer, 2.04 g (10.75 mmol) ofn-butylammonium n-butylcarbamate (white solid, melting point: 82-84° C.)was dissolved in 10 mL of methanol. 1.0 g (4.31 mmol) of silver oxidewas added and reaction was performed at room temperature. The reactionsolution was initially a black slurry but it turned transparent ascomplex was produced. After 2 hours of reaction, a colorless,transparent solution was obtained. The resultant solution was filteredwith a 0.45 micron membrane filter and the solvent was removed at vacuumto obtain white solid. The solid was dried and weighed to obtain 2.79 gof a silver complex (yield=92.0%). Most of the silver complex wasdecomposed below 130° C. to leave metallic silver. The silver contentwas 33.2 wt % (TGA analysis).

¹H NMR (CD₃OD, ppm), 0.92-0.97 (t, —CH₃), 1.37-1.46 (m, —CH₂), 1.52-1.59(m, —CH₂), 2.75-2.79 (t, —NCH₂), ¹³C NMR (CD₃OD, ppm), 161.46, 44.76,36.94, 21.05, 14.38

Example 5 Reaction of Silver Oxide with IsobutylammoniumIsobutylcarbamate

In a 50 mL Schlenk flask equipped with a stirrer, 2.04 g (10.75 mmol) ofisobutylammonium isobutylcarbamate (white solid, melting point: 80-82°C.) was dissolved in 10 mL of methanol. 1.0 g (4.31 mmol) of silveroxide was added and reaction was performed at room temperature. Thereaction solution was initially a black slurry but it turned transparentas complex was produced. After 2 hours of reaction, a colorless,transparent solution was obtained. The resultant solution was filteredwith a 0.45 micron membrane filter and the solvent was removed at vacuumto obtain white solid. The solid was dried and weighed to obtain 2.87 gof a silver complex (yield=94.4%). Most of the silver complex wasdecomposed below 130° C. to leave metallic silver. The silver contentwas 32.4 wt % (TGA analysis).

¹H NMR (CD₃OD, ppm), 0.96-0.98 (d, —CH₃), 1.67-1.74 (m, —CH), 2.59-2.88(dd, —CH₂), ¹³C NMR (CD₃OD, ppm), 161.48, 52.69, 33.16, 30.45, 20.42

Example 6 Reaction of Silver Oxide with t-butylammonium t-butylcarbamate

In a 50 mL Schlenk flask equipped with a stirrer, 2.04 g (10.75 mmol) oft-butylammonium t-butylcarbamate (white solid) was dissolved in 10 mL ofmethanol. 1.0 g (4.31 mmol) of silver oxide was added and reaction wasperformed at room temperature. The reaction solution was initially ablack slurry but it turned transparent as complex was produced. After 2hours of reaction, a colorless, transparent solution was obtained. Theresultant solution was filtered with a 0.45 micron membrane filter andthe solvent was removed at vacuum to obtain white solid. The solid wasdried and weighed to obtain 2.94 g of a silver complex (yield=97.0%).Most of the silver complex was decomposed below 130° C. to leavemetallic silver. The silver content was 31.4 wt % (TGA analysis).

¹H NMR (CD₃OD, ppm), 1.27 (s, —CH₃), ¹³C NMR (CD₃OD, ppm), 161.52,50.94, 32.28

Example 7 Reaction of Silver Carbonate with 2-ethylhexylammonium2-ethylhexylcarbamate

In a 50 mL Schlenk flask equipped with a stirrer, 3.27 g (10.80 mmol) of2-ethylhexylammonium 2-ethylhexylcarbamate (viscous liquid) wasdissolved in 10 mL of methanol and 1.0 g (3.60 mmol) of silver carbonatewas added. The reaction solution was initially a yellow slurry but itturned transparent as reaction proceeded. After 5 hours of reaction, ayellow, transparent solution was obtained, which confirmed production ofa complex. The resultant solution was filtered with a 0.45 micronmembrane filter and the solvent was removed at vacuum to obtain whitesolid. The solid was dried and weighed to obtain 4.18 g of a silvercomplex (yield=97.89%). Most of the silver complex was decomposed below130° C. to leave metallic silver. The silver content was 18.66 wt % (TGAanalysis).

¹H NMR (CD₃OD, ppm), 1.11-1.19 (m, —CH₃) 1.51-1.69 (m, —CH₂, —CH—),2.91-2.92, 3.23-3.25 (d, —NCH₂), 5.13 (t, —NH_(x)), ¹³C NMR (CD₃OD,ppm), 166.09, 47.60, 44.24, 31.76, 30.12, 24.77, 24.30, 14.64, 11.15

Example 8 Reaction of Silver Oxide with 2-methoxyethylammonium2-methoxyethylcarbamate

In a 50 mL Schlenk flask equipped with a stirrer, 2.17 g (11.18 mmol) of2-methoxyethylammonium 2-methoxyethylcarbamate (white solid, meltingpoint: 41-42° C.) was dissolved in 10 mL of methanol. 1.0 g (4.31 mmol)of silver oxide was added and reaction was performed at roomtemperature. The reaction solution was initially a black slurry but itturned transparent as complex was produced. After 2 hours of reaction, ayellow, transparent solution was obtained. The resultant solution wasfiltered with a 0.45 micron membrane filter and the solvent was removedat vacuum to obtain brown, viscous liquid. The liquid was dried andweighed to obtain 2.58 g of a silver complex (yield=81.4%). Most of thesilver complex was decomposed below 130° C. to leave metallic silver.The silver content was 35.9 wt % (TGA analysis). ¹H NMR (CD₃OD, ppm),2.93-2.96 (t, —NCH₂), 3.39 (s, —OCH₃), 3.48-3.50 (t, OCH₂), ¹³C NMR(CD₃OD, ppm), 161.48, 74.11, 59.35, 44.34

Example 9 Reaction of Silver Oxide with 2-hydroxyethylammonium2-hydroxyethylcarbamate

In a 50 mL Schlenk flask equipped with a stirrer, 1.78 g (12.90 mmol) of2-hydroxyethylammonium 2-hydroxyethylcarbamate was dissolved in 10 mL ofmethanol. 1.0 g (4.31 mmol) of silver oxide was added and reaction wasperformed at room temperature. The reaction solution was initially ablack slurry but it turned transparent as complex was produced. After 2hours of reaction, a yellow, transparent solution was obtained. Theresultant solution was filtered with a 0.45 micron membrane filter andthe solvent was removed at vacuum to obtain brown, viscous liquid. Theliquid was dried and weighed to obtain 2.50 g of a silver complex(yield=90.1%). Most of the silver complex was decomposed below 130° C.to leave metallic silver. The silver content was 37.1 wt % (TGAanalysis).

¹H NMR (CD₃OD, ppm), 2.82-2.85 (t, —NCH₂), 3.61-3.64 (t, OCH₂), ¹³C NMR(CD₃OD, ppm), 166.16, 63.70, 46.12

Example 10 Reaction of Silver Oxide with 2-cyanoethylammonium2-cyanoethylcarbamate

In a 50 mL Schlenk flask equipped with a stirrer, 2.40 g (12.90 mmol) of2-cyanoethylammonium 2-cyanoethylcarbamate (white solid, melting point:70-72° C.) was dissolved in 10 mL of methanol. 1.0 g (4.31 mmol) ofsilver oxide was added and reaction was performed at room temperature.The reaction solution was initially a black slurry but it turnedtransparent as complex was produced. After 2 hours of reaction, acolorless, transparent solution was obtained. The resultant solution wasfiltered with a 0.45 micron membrane filter and the solvent was removedat vacuum to obtain white solid. The solid was dried and weighed toobtain 3.06 g of a silver complex (yield=90.0%). About 60% of the silvercomplex was decomposed below 150° C. to leave metallic silver andunreacted organic materials. Most of the silver complex was decomposedbelow 250° C. to leave metallic silver. The silver content was 28.7 wt %(TGA analysis).

Example 11 Reaction of Silver Oxide with MorpholiniumMorpholinecarbamate

In a 50 mL Schlenk flask equipped with a stirrer, 2.81 g (12.90 mmol) ofmorpholinium morpholinecarbamate was dissolved in 10 mL of methanol. 1.0g (4.31 mmol) of silver oxide was added and reaction was performed atroom temperature. The reaction solution was initially a black slurry butit turned transparent as complex was produced. After 2 hours ofreaction, a yellow, transparent solution was obtained. The resultantsolution was filtered with a 0.45 micron membrane filter and the solventwas removed at vacuum to obtain gray solid. The solid was dried andweighed to obtain 3.29 g of a silver complex (yield=86.4%). Most of thesilver complex was decomposed below 130° C. to leave metallic silver.The silver content was 28.3 wt % (TGA analysis).

Example 12 Reaction of Silver Oxide with HexamethyleneiminiumHexamethyleneiminecarbamate

In a 50 mL Schlenk flask equipped with a stirrer, 3.13 g (12.90 mmol) ofhexamethyleneiminium hexamethyleneiminecarbamate was dissolved in 10 mLof methanol. 1.0 g (4.31 mmol) of silver oxide was added and reactionwas performed at room temperature. The reaction solution was initially ablack slurry but it turned transparent as complex was produced. After 2hours of reaction, a yellow, transparent solution was obtained. Theresultant solution was filtered with a 0.45 micron membrane filter andthe solvent was removed at vacuum to obtain brown liquid. The liquid wasdried and weighed to obtain 3.29 g of a silver complex (yield=86.8%).Most of the silver complex was decomposed below 130° C. to leavemetallic silver. The silver content was 25.9 wt % (TGA analysis).

Example 13 Reaction of Silver Oxide with Ammonium Carbamate

In a 250 mL Schlenk flask equipped with a stirrer, 6.71 g (86 mmol) ofammonium carbamate and 15 g of isopropylamine (0.25 mol) were dissolvedin 50 mL of methanol. 10.0 g (43.1 mmol) of silver oxide was added andreaction was performed at room temperature. The reaction solution wasinitially a black slurry but it turned transparent as complex wasproduced. After 3 hours of reaction, a colorless, transparent solutionwas obtained. The resultant solution was filtered with a 0.45 micronmembrane filter and the solvent was removed at vacuum to obtain whitesolid. The solid was dried and weighed to obtain 26.90 g of a silvercomplex (yield=84.9%). Most of the silver complex was decomposed below130° C. to leave metallic silver. The silver content was 42.0 wt % (TGAanalysis).

Example 14 Reaction of Silver Carbonate with Ammonium Carbamate

In a 250 mL Schlenk flask equipped with a stirrer, 3.36 g (43 mmol) ofammonium carbamate and 15 g of isopropylamine (0.25 mol) were dissolvedin 50 mL of methanol. 11.88 g (43.1 mmol) of silver carbonate was addedand reaction was performed at room temperature. The reaction solutionwas initially a yellow slurry but it turned transparent as complex wasproduced. After 6 hours of reaction, a colorless, transparent solutionwas obtained. The resultant solution was filtered with a 0.45 micronmembrane filter and the solvent was removed at vacuum to obtain whitesolid. The solid was dried and weighed to obtain 25.60 g of a silvercomplex (yield=84.5%). Most of the silver complex was decomposed below130° C. to leave metallic silver. The silver content was 45.8 wt % (TGAanalysis).

Example 15 Reaction of Silver Oxide with 2-ethylhexylammonium2-ethylhexylcarbamate

In a 50 mL Schlenk flask equipped with a stirrer, 3.25 g (10.75 mmol) of2-ethylhexylammonium 2-ethylhexylcarbamate (viscous liquid) wasdissolved in 10 mL of tetrahydrofuran (THF). 1.0 g (4.31 mmol) of silveroxide was added and reaction was performed at room temperature. Thereaction solution was initially a black slurry but it turned transparentas complex was produced. After 2 hours of reaction, a yellow,transparent solution was obtained. The resultant solution was filteredwith a 0.45 micron membrane filter and the solvent was removed at vacuumto obtain white solid. The solid was dried and weighed to obtain 3.58 gof a silver complex (yield=88.23%). Most of the silver complex wasdecomposed below 130° C. to leave metallic silver. The silver contentwas 25.97 wt % (TGA analysis).

Example 16 Reaction of Silver Oxide with 2-ethylhexylammonium2-ethylhexylcarbamate

In a 50 mL Schlenk flask equipped with a stirrer, 3.25 g (10.75 mmol) of2-ethylhexylammonium 2-ethylhexylcarbamate (viscous liquid) wasdissolved in 10 mL of ethyl acetate. 1.0 g (4.31 mmol) of silver oxidewas added and reaction was performed at room temperature. The reactionsolution was initially a black slurry but it turned transparent ascomplex was produced. After 2 hours of reaction, a colorless,transparent solution was obtained. The resultant solution was filteredwith a 0.45 micron membrane filter and the solvent was removed at vacuumto obtain white solid. The solid was dried and weighed to obtain 3.53 gof a silver complex (yield=83.17%). Most of the silver complex wasdecomposed below 130° C. to leave metallic silver. The silver contentwas 26.34 wt % (TGA analysis).

Example 17 Reaction of Silver Oxide with 2-ethylhexylammonium2-ethylhexylcarbamate

To a 50 mL Schlenk flask equipped with a stirrer was added 3.90 g (12.90mmol) of 2-ethylhexylammonium 2-ethylhexylcarbamate (viscous liquid).1.0 g (4.31 mmol) of silver oxide was added and reaction was performedat room temperature. The reaction solution was initially a black slurrybut it turned transparent as complex was produced. After 2 hours ofreaction, a yellow, transparent solution was obtained. The resultantsolution was filtered with a 0.45 micron membrane filter and kept atvacuum to obtain white solid. The solid was dried and weighed to obtain3.58 g of a silver complex (yield=88.23%). Most of the silver complexwas decomposed below 130° C. to leave metallic silver. The silvercontent was 25.97 wt % (TGA analysis).

Example 18 Reaction of Silver Oxide with aminoethylammoniumaminoethylcarbamate

In a 50 mL Schlenk flask equipped with a stirrer, 1.763 g (10.75 mmol)of aminoethylammonium aminoethylcarbamate (white solid) was dissolved in10 mL of methanol. 1.0 g (4.31 mmol) of silver oxide was added andreaction was performed at room temperature. The reaction solution wasinitially a black slurry but it turned transparent as complex wasproduced. After 2 hours of reaction, a colorless, transparent solutionwas obtained. The resultant solution was filtered with a 0.45 micronmembrane filter and the solvent was removed at vacuum to obtain black,viscous liquid. The liquid was dried and weighed to obtain 2.21 g of asilver complex (yield=79.99%). Most of the silver complex was decomposedbelow 130° C. to leave metallic silver. The silver content was 42.12 wt% (TGA analysis).

Example 19 Reaction of Silver Oxide with 2-ethylhexylammonium2-ethylhexylcarbamate and aminoethylammonium aminoethylcarbamate

In a 50 mL Schlenk flask equipped with a stirrer, 3.07 g (10.80 mmol) ofa 6:1 (molar ratio) mixture of 2-ethylhexylammonium2-ethylhexylcarbamate and aminoethylammonium aminoethylcarbamate wasdissolved in 10 mL of methanol. 1.0 g (4.31 mmol) of silver oxide wasadded and reaction was performed at room temperature. The reactionsolution was initially a black slurry but it turned transparent ascomplex was produced. After 2 hours of reaction, a colorless,transparent solution was obtained. The resultant solution was filteredwith a 0.45 micron membrane filter and the solvent was removed at vacuumto obtain orange, viscous liquid. The liquid was dried and weighed toobtain 3.85 g of a silver complex (yield=94.59%). Most of the silvercomplex was decomposed below 130° C. to leave metallic silver. Thesilver content was 24.20 wt % (TGA analysis).

Example 20 Reaction of Silver Sulfate with 2-ethylhexylammonium2-ethylhexylcarbamate

In a 50 mL Schlenk flask equipped with a stirrer, 2.42 g (8.00 mmol) of2-ethylhexylammonium 2-ethylhexylcarbamate (viscous liquid) wasdissolved in 10 mL of methanol. 1.0 g (3.2 mmol) of silver sulfate wasadded and reaction was performed at room temperature. The reactionsolution was initially a white slurry but it turned transparent ascomplex was produced. After 2 hours, a completely transparent solutionwas obtained. The resultant solution was filtered with a 0.45 micronmembrane filter and the solvent was removed at vacuum to obtain whitesolid. The solid was recrystallized in ethyl acetate, dried and weighedto obtain 3.15 g of a silver complex (yield=92.3%). Most of the silvercomplex was decomposed below 130° C. to leave metallic silver. Thesilver content was 21.35 wt % (TGA analysis).

Example 21 Reaction of Silver Nitrate with 2-ethylhexylammonium2-ethylhexylcarbamate

In a 50 mL Schlenk flask equipped with a stirrer, 2.23 g (7.37 mmol) of2-ethylhexylammonium 2-ethylhexylcarbamate (viscous liquid) wasdissolved in 10 mL of methanol. 1.0 g (5.9 mmol) of silver nitrate wasadded and reaction was performed at room temperature. The reactionsolution was initially a white slurry but it turned transparent ascomplex was produced. After 2 hours, a completely transparent solutionwas obtained. The resultant solution was filtered with a 0.45 micronmembrane filter and the solvent was removed at vacuum to obtain whitesolid. The solid was recrystallized in ethyl acetate, dried and weighedto obtain 2.76 g of a silver complex (yield=85.6%). Most of the silvercomplex was decomposed below 130° C. to leave metallic silver. Thesilver content was 22.73 wt % (TGA analysis).

Example 22 Reaction of Silver Cyanide with 2-ethylhexylammonium2-ethylhexylcarbamate

In a 50 mL Schlenk flask equipped with a stirrer, 2.83 g (9.37 mmol) of2-ethylhexylammonium 2-ethylhexylcarbamate (viscous liquid) wasdissolved in 10 mL of dimethylsulfoxide (DMSO). 1 g (7.5 mmol) of silvercyanide was added and reaction was performed at room temperature. Thereaction solution was initially a white slurry but it turned transparentas complex was produced. After 2 hours, a completely transparentsolution was obtained. The resultant solution was filtered with a 0.45micron membrane filter and the solvent was removed at vacuum to obtainwhite solid. The solid was recrystallized in ethyl acetate, dried andweighed to obtain 3.15 g of a silver complex (yield=82.42%). Most of thesilver complex was decomposed below 130° C. to leave metallic silver.The silver content was 25.43 wt % (TGA analysis).

Example 23 Reaction of Silver Oxide with 2-ethylhexylammonium2-ethylhexylcarbonate

In a 50 mL Schlenk flask equipped with a stirrer, 3.72 g (11.61 mmol) of2-ethylhexylammonium 2-ethylhexylcarbamate (viscous liquid) wasdissolved in 10 mL of methanol. 1.0 g (4.31 mmol) of silver oxide wasadded and reaction was performed at room temperature. The reactionsolution was initially a black slurry but it turned transparent ascomplex was produced. After 2 hours, a colorless, transparent solutionwas obtained. The resultant solution was filtered with a 0.45 micronmembrane filter to remove unreacted silver oxide particles and thesolvent was removed at vacuum to obtain white solid. The solid was driedand weighed to obtain 4.02 g of a silver complex (yield=85.2%). Thesilver complex had a melting point of 55-57° C. (DSC=57.34° C.) and asilver content of 21.43 wt % (TGA analysis). ¹H NMR (CD₃OD, ppm),0.87-0.99 (m, —CH₃) 1.31-1.47 (m, —CH₂, —CH—), 2.69-2.70, 3.01-3.02 (d,—NCH₂), 4.90 (s, —NH₂), ¹³C NMR (CD₃OD, ppm), 165.00, 47.70, 44.25,31.73, 30.90, 24.73, 24.29, 14.68, 11.16

Example 24 Reaction of Silver Oxide with 2-ethylhexylammoniumbicarbonate

In a 50 mL Schlenk flask equipped with a stirrer, 4.86 g (25.37 mmol) of2-ethylhexylammonium bicarbonate (viscous liquid) was dissolved in 10 mLof methanol. 1.0 g (4.31 mmol) of silver oxide was added and reactionwas performed at room temperature. The reaction solution was initially ablack slurry but it turned transparent as complex was produced. After 2hours, a colorless, transparent solution was obtained. The resultantsolution was filtered with a 0.45 micron membrane filter and the solventwas removed at vacuum to obtain white solid. The solid was dried andweighed to obtain 4.33 g of a silver complex (yield=73.9%). The silvercomplex had a melting point of 56-57° C. (DSC=57.66° C.) and a silvercontent of 21.48 wt % (TGA analysis).

¹H NMR (CD₃OD, ppm), 0.93-1.08 (m, —CH₃) 1.31-1.64 (m, —CH₂, —CH—),2.93-2.94, 3.25-3.26 (d, —NCH₂), 5.13 (s, —NH₂), ¹³C NMR (CD₃OD, ppm),165.56, 47.73, 44.23, 31.713, 30.08, 24.72, 24.28, 14.69, 11.17

Example 25 Reaction of Silver Oxide with isopropylammoniumisopropylcarbonate

In a 50 mL Schlenk flask equipped with a stirrer, 2.01 g (11.18 mmol) ofisopropylammonium isopropylcarbonate was dissolved in 10 mL of methanoland 1.0 g (4.31 mmol) of silver oxide was added. The reaction solutionwas initially a black slurry but it turned transparent as complex wasproduced. After 2 hours, a colorless, transparent solution was obtained.The resultant solution was filtered with a 0.45 micron membrane filterand the solvent was removed at vacuum to obtain white solid. The solidwas dried and weighed to obtain 2.41 g of a silver complex(yield=80.2%). Most of the silver complex was decomposed below 130° C.and the silver content was 38.6 wt % (TGA analysis).

Example 26 Reaction of Silver Carbonate with IsopropylammoniumIsopropylcarbonate

In a 50 mL Schlenk flask equipped with a stirrer, 2.07 g (11.52 mmol) ofisopropylammonium isopropylcarbonate was dissolved in 10 mL of methanoland 1.0 g (3.60 mmol) of silver carbonate was added. The reactionsolution was initially a yellow slurry but it turned transparent ascomplex was produced. After 6 hours, a colorless, transparent solutionwas obtained. The resultant solution was filtered with a 0.45 micronmembrane filter and the solvent was removed at vacuum to obtain whitesolid. The solid was dried and weighed to obtain 2.42 g of a silvercomplex (yield=78.8%). Most of the silver complex was decomposed below130° C. and the silver content was 32.23 wt % (TGA analysis).

Example 27 Reaction of Silver Carbonate with 2-ethylhexylammonium2-ethylhexylcarbonate

In a 50 mL Schlenk flask equipped with a stirrer, 3.46 g (14.4 mmol) of2-ethylhexylammonium 2-ethylhexylcarbonate (viscous liquid) wasdissolved in 10 mL of methanol and 1.0 g (3.60 mmol) of silver carbonatewas added. The reaction solution was initially a yellow slurry but itturned transparent as complex was produced. After 6 hours, a yellow,transparent solution was obtained. The resultant solution was filteredwith a 0.45 micron membrane filter and the solvent was removed at vacuumto obtain white solid. The solid was dried and weighed to obtain 4.15 gof a silver complex (yield=93.04%). Most of the silver complex wasdecomposed below 130° C. and the silver content was 18.79 wt % (TGAanalysis).

Example 28 Reaction of Silver Oxide with Isopropylammonium Bicarbonate

In a 50 mL Schlenk flask equipped with a stirrer, 2.97 g (24.51 mmol) ofisopropylammonium bicarbonate (melting point: 53-54° C.) was dissolvedin 10 mL of methanol and 1.0 g (4.31 mmol) of silver oxide was added.The reaction solution was initially a black slurry but it turnedtransparent as complex was produced. After 2 hours, a colorless,transparent solution was obtained. The resultant solution was filteredwith a 0.45 micron membrane filter and the solvent was removed at vacuumto obtain white solid. The solid was dried and weighed to obtain 2.41 gof a silver complex (yield=60.7%). The silver complex had a meltingpoint of 68-70° C. (DSC=70.49° C.). Most of the silver complex wasdecomposed below 130° C. to leave metallic silver and the silver contentwas 38.58 wt % (TGA analysis).

Example 29 Reaction of Silver Oxide with Ammonium Carbonate

In a 250 mL Schlenk flask equipped with a stirrer, 8.26 g (86 mmol) ofammonium carbonate and 15 g (0.25 mol) of isopropyl amine were dissolvedin 50 mL of methanol and 10.0 g (43.1 mmol) of silver oxide was added.The reaction solution was initially a black slurry but it turnedtransparent as complex was produced. After 2 hours, a colorless,transparent solution was obtained. The resultant solution was filteredwith a 0.45 micron membrane filter and the solvent was removed at vacuumto obtain white solid. The solid was dried and weighed to obtain 28.38 gof a silver complex (yield=85.5%). The silver complex had a meltingpoint (DSC) of 63.38° C. Most of the silver complex was decomposed below130° C. to leave metallic silver and the silver content was 46.3 wt %(TGA analysis).

Example 30 Reaction of Silver Carbonate with Ammonium Carbonate

In a 250 mL Schlenk flask equipped with a stirrer, 4.13 g (43 mmol) ofammonium carbonate and 15 g (0.25 mol) of isopropyl amine were dissolvedin 50 mL of methanol and 11.88 g (43.1 mmol) of silver carbonate wasadded. The reaction solution was initially a yellow slurry but it turnedtransparent as complex was produced. After 6 hours, a colorless,transparent solution was obtained. The resultant solution was filteredwith a 0.45 micron membrane filter and the solvent was removed at vacuumto obtain white solid. The solid was dried and weighed to obtain 26.71 gof a silver complex (yield=85.9%). Most of the silver complex wasdecomposed below 130° C. to leave metallic silver and the silver contentwas 47.8 wt % (TGA analysis).

Example 31 Reaction of Silver Oxide with Ammonium Bicarbonate

In a 250 mL Schlenk flask equipped with a stirrer, 6.8 g (86 mmol) ofammonium bicarbonate and 15 g (0.25 mol) of isopropyl amine weredissolved in 50 mL of methanol and 10.0 g (43.1 mmol) of silver oxidewas added. The reaction solution was initially a black slurry but itturned transparent as complex was produced. After 3 hours, a colorless,transparent solution was obtained. The resultant solution was filteredwith a 0.45 micron membrane filter and the solvent was removed at vacuumto obtain white solid. The solid was dried and weighed to obtain 26.55 gof a silver complex (yield=83.5%). Most of the silver complex wasdecomposed below 130° C. to leave metallic silver and the silver contentwas 46.8 wt % (TGA analysis).

Example 32 Reaction of Silver Carbonate with Ammonium Bicarbonate

In a 250 mL Schlenk flask equipped with a stirrer, 3.4 g (43 mmol) ofammonium bicarbonate and 15 g (0.25 mol) of isopropyl amine weredissolved in 50 mL of methanol and 11.88 g (43.1 mmol) of silvercarbonate was added. The reaction solution was initially a yellow slurrybut it turned transparent as complex was produced. After 6 hours, acolorless, transparent solution was obtained. The resultant solution wasfiltered with a 0.45 micron membrane filter and the solvent was removedat vacuum to obtain white solid. The solid was dried and weighed toobtain 26.20 g of a silver complex (yield=86.2%). Most of the silvercomplex was decomposed below 130° C. to leave metallic silver and thesilver content was 48.2 wt % (TGA analysis).

Example 33 Reaction of Silver Oxide with 2-methoxyethylammoniumBicarbonate

In a 50 mL Schlenk flask equipped with a stirrer, 3.24 g (23.65 mmol) of2-methoxyethylammonium bicarbonate (viscous liquid) was dissolved in 10mL of methanol and 1.0 g (4.31 mmol) of silver oxide was added. Thereaction solution was initially a black slurry but it turned transparentas complex was produced. After 2 hours, a yellow, transparent solutionwas obtained. The resultant solution was filtered with a 0.45 micronmembrane filter and the solvent was removed at vacuum to obtain yellow,viscous liquid. The liquid was dried and weighed to obtain 3.01 g of asilver complex (yield=70.75%). Most of the silver complex was decomposedbelow 130° C. to leave metallic silver and the silver content was 31.08wt % (TGA analysis).

Example 34 Reaction of Silver Carbonate with 2-methoxyethylammoniumBicarbonate

In a 50 mL Schlenk flask equipped with a stirrer, 3.78 g (27.54 mmol) of2-methoxyethylammonium bicarbonate (viscous liquid) was dissolved in 10mL of methanol and 1.0 g (3.60 mmol) of silver carbonate was added. Thereaction solution was initially a yellow slurry but it turnedtransparent as complex was produced. After 2 hours, a yellow,transparent solution was obtained. The resultant solution was filteredwith a 0.45 micron membrane filter and the solvent was removed at vacuumto obtain yellow, viscous liquid. The liquid was dried and weighed toobtain 3.28 g of a silver complex (yield=68.61%). Most of the silvercomplex was decomposed below 130° C. to leave metallic silver and thesilver content was 23.78 wt % (TGA analysis).

Example 35 Reaction of Silver Oxide with Octylammonium Bicarbonate

In a 50 mL Schlenk flask equipped with a stirrer, 3.07 g (24.73 mmol) ofoctylammonium bicarbonate (white solid) was dissolved in 10 mL ofmethanol and 1.0 g (4.31 mmol) of silver oxide was added. The reactionsolution was initially a black slurry but it turned transparent ascomplex was produced. After 2 hours, a colorless, transparent solutionwas obtained. The resultant solution was filtered with a 0.45 micronmembrane filter and the solvent was removed at vacuum to obtain whitesolid. The solid was dried and weighed to obtain 3.81 g of a silvercomplex (yield=93.61%). Most of the silver complex was decomposed below130° C. to leave metallic silver and the silver content was 24.40 wt %(TGA analysis).

Example 36 Reaction of Silver Oxide with Isobutylammonium Bicarbonate

In a 50 mL Schlenk flask equipped with a stirrer, 3.20 g (23.65 mmol) ofisobutylammonium bicarbonate (white solid) was dissolved in 10 mL ofmethanol and 1.0 g (4.31 mmol) of silver oxide was added. The reactionsolution was initially a black slurry but it turned transparent ascomplex was produced. After 2 hours, a colorless, transparent solutionwas obtained. The resultant solution was filtered with a 0.45 micronmembrane filter and the solvent was removed at vacuum to obtain whitesolid. The solid was dried and weighed to obtain 3.21 g of a silvercomplex (yield=76.42%). Most of the silver complex was decomposed below130° C. to leave metallic silver and the silver content was 28.97 wt %(TGA analysis).

Example 37 Reaction of Silver Oxide with n-Butylammonium Bicarbonate

In a 50 mL Schlenk flask equipped with a stirrer, 3.20 g (23.65 mmol) ofviscous n-butylammonium bicarbonate was dissolved in 10 mL of methanoland 1.0 g (4.31 mmol) of silver oxide was added. The reaction solutionwas initially a black slurry but it turned transparent as complex wasproduced. After 6 hours, a colorless, transparent solution was obtained.The resultant solution was filtered with a 0.45 micron membrane filterand the solvent was removed at vacuum to obtain white solid. The solidwas dried and weighed to obtain 3.49 g of a silver complex(yield=83.09%). Most of the silver complex was decomposed below 130° C.to leave metallic silver and the silver content was 26.72 wt % (TGAanalysis).

Example 38 Reaction of Silver Oxide with Morpholinium Bicarbonate

In a 50 mL Schlenk flask equipped with a stirrer, 3.53 g (23.65 mmol) ofmorpholinium bicarbonate (white solid) was dissolved in 10 mL ofmethanol and 1.0 g (4.31 mmol) of silver oxide was added. The reactionsolution was initially a black slurry but it turned transparent ascomplex was produced. After 2 hours, a yellow, transparent solution wasobtained. The resultant solution was filtered with a 0.45 micronmembrane filter and the solvent was removed at vacuum to obtain whitesolid. The solid was dried and weighed to obtain 3.16 g of a silvercomplex (yield=69.75%). Most of the silver complex was decomposed below130° C. to leave metallic silver and the silver content was 29.49 wt %(TGA analysis).

Example 39 Reaction of Silver Oxide with 2-ethylhexylammonium2-ethylhexylcarbonate

In a 50 mL Schlenk flask equipped with a stirrer, 4.13 g (12.90 mmol) of2-ethylhexylammonium 2-ethylhexylcarbonate (viscous liquid) wasdissolved in 10 mL of tetrahydrofuran (THF) and 1.0 g (4.31 mmol) ofsilver oxide was added. The reaction solution was initially a blackslurry but it turned transparent as complex was produced. After 2 hours,a yellow, transparent solution was obtained. The resultant solution wasfiltered with a 0.45 micron membrane filter and the solvent was removedat vacuum to obtain white solid. The solid was dried and weighed toobtain 4.05 g of a silver complex (yield=78.84%). Most of the silvercomplex was decomposed below 130° C. to leave metallic silver and thesilver content was 22.96 wt % (TGA analysis).

Example 40 Reaction of Silver Oxide with 2-ethylhexylammonium2-ethylhexylcarbonate

In a 50 mL Schlenk flask equipped with a stirrer, 4.13 g (12.90 mmol) of2-ethylhexylammonium 2-ethylhexylcarbonate (viscous liquid) wasdissolved in 10 mL of ethyl acetate and 1.0 g (4.31 mmol) of silveroxide was added. The reaction solution was initially a black slurry butit turned transparent as complex was produced. After 2 hours, acolorless, transparent solution was obtained. The resultant solution wasfiltered with a 0.45 micron membrane filter and the solvent was removedat vacuum to obtain white solid. The solid was dried and weighed toobtain 3.96 g of a silver complex (yield=77.19%). Most of the silvercomplex was decomposed below 130° C. to leave metallic silver and thesilver content was 23.48 wt % (TGA analysis).

Example 41 Reaction of Silver Oxide with 2-ethylhexylammonium2-ethylhexylcarbonate

Into a 50 mL Schlenk flask equipped with a stirrer were added 4.13 g(12.90 mmol) of 2-ethylhexylammonium 2-ethylhexylcarbonate (viscousliquid) and 1.0 g (4.31 mmol) of silver oxide. The reaction solution wasinitially a black slurry but it turned transparent as complex wasproduced. After 2 hours, a yellow, transparent solution was obtained.The resultant solution was filtered with a 0.45 micron membrane filterand the solvent was removed at vacuum to obtain white solid. The solidwas dried and weighed to obtain 3.96 g of a silver complex(yield=77.19%). Most of the silver complex was decomposed below 130° C.to leave metallic silver and the silver content was 23.48 wt % (TGAanalysis).

Example 42 Reaction of Silver Oxide with AminoethylammoniumAminoethylcarbonate

In a 50 mL Schlenk flask equipped with a stirrer, 2.35 g (12.90 mmol) ofaminoethylammonium aminoethylcarbonate (white solid) was dissolved in 10mL of methanol and 1.0 g (4.31 mmol) of silver oxide was added. Thereaction solution was initially a black slurry but it turned transparentas complex was produced. After 2 hours, a colorless, transparentsolution was obtained. The resultant solution was filtered with a 0.45micron membrane filter and the solvent was removed at vacuum to obtainblack, viscous liquid. The liquid was dried and weighed to obtain 2.42 gof a silver complex (yield=72.23%). Most of the silver complex wasdecomposed below 130° C. to leave metallic silver and the silver contentwas 38.45 wt % (TGA analysis).

Example 43 Reaction of Silver Oxide with 2-ethylhexylammonium2-ethylhexylcarbonate and Aminoethylammonium Aminoethylcarbonate

In a 50 mL Schlenk flask equipped with a stirrer, 3.87 g (12.9 mmol) ofa 6:1 (molar ratio) mixture of 2-ethylhexylammonium2-ethylhexylcarbonate and aminoethylammonium aminoethylcarbonate wasdissolved in 10 mL of methanol and 1.0 g (4.31 mmol) of silver oxide wasadded. The reaction solution was initially a black slurry but it turnedtransparent as complex was produced. After 2 hours of reaction, acolorless, transparent solution was obtained. The resultant solution wasfiltered with a 0.45 micron membrane filter and the solvent was removedat vacuum to obtain orange, viscous liquid. The liquid was dried andweighed to obtain 3.05 g of a silver complex (yield=78.85%). Most of thesilver complex was decomposed below 130° C. to leave metallic silver.The silver content was 30.41 wt % (TGA analysis).

Example 44 Reaction of Silver Sulfate with 2-ethylhexylammonium2-ethylhexylcarbonate

In a 50 mL Schlenk flask equipped with a stirrer, 3.07 g (9.60 mmol) of2-ethylhexylammonium 2-ethylhexylcarbonate (viscous liquid) wasdissolved in 10 mL of methanol and 1.0 g (3.2 mmol) of silver sulfatewas added. The reaction solution was initially a white slurry but itturned transparent as complex was produced. After 2 hours, a completelytransparent solution was obtained. The resultant solution was filteredwith a 0.45 micron membrane filter and the solvent was removed at vacuumto obtain white solid. The solid was recrystallized in ethyl acetate,dried and weighed to obtain 3.55 g of a silver complex (yield=87.2%).Most of the silver complex was decomposed below 130° C. to leavemetallic silver and the silver content was 19.52 wt % (TGA analysis).

Example 45 Reaction of Silver Nitrate with 2-ethylhexylammonium2-ethylhexylcarbonate

In a 50 mL Schlenk flask equipped with a stirrer, 2.84 g (8.86 mmol) of2-ethylhexylammonium 2-ethylhexylcarbonate (viscous liquid) wasdissolved in 10 mL of methanol and 1.0 g (5.9 mmol) of silver nitratewas added. The reaction solution was initially a white slurry but itturned transparent as complex was produced. After 2 hours, a completelytransparent solution was obtained. The resultant solution was filteredwith a 0.45 micron membrane filter and the solvent was removed at vacuumto obtain white solid. The solid was recrystallized in ethyl acetate,dried and weighed to obtain 3.12 g of a silver complex (yield=81.34%).Most of the silver complex was decomposed below 130° C. to leavemetallic silver and the silver content was 19.88 wt % (TGA analysis).

Example 46 Reaction of Silver Cyanide with 2-ethylhexylammonium2-ethylhexylcarbonate

In a 50 mL Schlenk flask equipped with a stirrer, 3.59 g (11.20 mmol) of2-ethylhexylammonium 2-ethylhexylcarbonate (viscous liquid) wasdissolved in 10 mL of methanol and 1.0 g (7.5 mmol) of silver cyanidewas added. The reaction solution was initially a white slurry but itturned transparent as complex was produced. After 2 hours, a completelytransparent solution was obtained. The resultant solution was filteredwith a 0.45 micron membrane filter and the solvent was removed at vacuumto obtain white solid. The solid was recrystallized in ethyl acetate,dried and weighed to obtain 3.93 g of a silver complex (yield=85.62%).Most of the silver complex was decomposed below 130° C. to leavemetallic silver and the silver content was 20.37 wt % (TGA analysis).

From the silver contents of the prepared compounds, m values werecalculated. They are given in Table 1 below.

TABLE 1 Example No. m value  1 1.3  2 1.1  3 1.1  4 1.1  5 1.2  6 1.2  71.6  8 1.0  9 1.1 10 1.4 11 1.1 12 1.1 13 1.9 14 1.6 15 1.0 16 1.0 171.0 18 0.9 19 0.7 20 1.3 21 1.2 22 1.1 23 1.2 24 2.1 25 1.0 26 1.3 271.5 28 1.6 29 1.3 30 1.2 31 1.6 32 1.5 33 1.8 34 2.5 35 1.8 36 2.0 372.2 38 1.6 39 1.1 40 1.1 41 1.1 42 1.0 43 0.8 44 1.4 45 1.4 46 1.3 — — ——

Example 47

4 g of the silver complex prepared in Example 1 was dissolved in 5 g ofbutyl alcohol. After adjusting the viscosity to 500 cps, pattering wasperformed on a coated paper (ITP20HPG or ITP20SPH; InkTec) on a silkscreen patterned to 320 meshes using a stainless steel (SUS) wire cloth.After heat treatment at 100° C. for 5 minutes and then at 130° C. for 10minutes, a metal pattern having a conductivity of 400-500 mΩ/□ wasobtained.

Example 48

4 g of the silver complex prepared in Example 1 was dissolved in 10 g ofisopropyl alcohol. After adjusting the viscosity to 13 cps, patteringwas performed on a PET film for one time using an ink-jet printer. Afterheat treatment at 80° C. for 5 minutes and then at 130° C. for 10minutes, a metal pattern having a conductivity of 200-300 mΩ/□ wasobtained.

Example 49

4 g of the silver complex prepared in Example 23 was dissolved in 5 g of2-hexyl alcohol. After adjusting the viscosity to 500 cps, pattering wasperformed on a coated paper (ITP20HPG or ITP20SPH; InkTec) on a 320-meshpatterned silk screen. After heat treatment at 100° C. for 5 minutes andthen at 130° C. for 10 minutes, a metal pattern having a conductivity of400-500 mΩ/□ was obtained.

Example 50

4 g of the silver complex prepared in Example 24 was dissolved in 10 gof butyl alcohol. After adjusting the viscosity to 13 cps, pattering wasperformed on a PET film for one time using an ink-jet printer. Afterheat treatment at 80° C. for 5 minutes and then at 130° C. for 10minutes, a metal pattern having a conductivity of 200-300 mΩ/□ wasobtained.

INDUSTRIAL APPLICABILITY

The present invention provides a useful organic silver complex byreacting the silver compound represented by the formula 2 with theammonium carbamate compound or the ammonium carbonate compoundrepresented by the formula 3, 4 or 5.

As the TGA analysis shows, the organic silver complex of the presentinvention is decomposed at a very low temperature to give pure metalfilm or powder. So, it can be processed into a variety of metallicsilver films or formed into an ultrathin film by deposition under highvacuum. Thus, it can be used in plating, medicine, photography,electricity and electronics, fibers, detergents, household appliances,organics and polymer synthesis as catalyst or may be used in preparationof silver powder, paste and nanoparticle. Particularly, it may beutilized in low-resistance metal wirings, printed circuit boards (PCB),flexible printed circuit boards (FPC), antennas for radio frequencyidentification (RFID) tags, plasma display panels (PDP), liquid crystaldisplays (TFT-LCD), organic light emitting diodes (OLED), flexibledisplays, organic thin-film transistors (OTFT), electrodes, etc. asprecursor material for metal patterning by chemical vapor deposition(CVD), plasma vapor deposition, sputtering, electroplating, lithography,electron beam, laser, etc. In addition, the organic silver complexsolution of the present invention may be spin coated, roll coated, spraycoated, dip coated, flow coated, ink-jet printed, offset printed, screenprinted, gravure printed or flexo printed on such a substrate as glass,silicon wafer and polymer film like polyester or polyimide, paper, etc.and reduced, oxidized or heat-treated to form a metal or metal oxidepattern.

While the present invention has been described in detail with referenceto the preferred embodiments, those skilled in the art will appreciatethat various modifications and substitutions can be made thereto withoutdeparting from the spirit and scope of the present invention as setforth in the appended claims.

The invention claimed is:
 1. A method for preparing a silver complex byreacting silver oxide with a mixture of ammonium carbamate and isopropylamine at room temperature in the presence of methanol.